CN119858366A - Material with sterilization and peculiar smell removal functions for automobile lining and preparation method thereof - Google Patents

Material with sterilization and peculiar smell removal functions for automobile lining and preparation method thereof Download PDF

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Publication number
CN119858366A
CN119858366A CN202510337141.0A CN202510337141A CN119858366A CN 119858366 A CN119858366 A CN 119858366A CN 202510337141 A CN202510337141 A CN 202510337141A CN 119858366 A CN119858366 A CN 119858366A
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lysozyme
silver
mof
reaction
fabric
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CN119858366B (en
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朱成业
冯亮
林杰
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Jinhua City Waldorf Auto Interior Parts Co ltd
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Jinhua City Waldorf Auto Interior Parts Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
    • B60R13/0212—Roof or head liners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B13/00—Treatment of textile materials with liquids, gases or vapours with aid of vibration
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)

Abstract

本发明提供了一种具有杀菌除异味的汽车内衬用材料及其制备方法。汽车内衬用材料包括依次设置的表面层、功能层和底层，所述功能层是将面料经过MOF‑溶菌酶材料表面处理得到。通过银离子与二甲基咪唑形成的银基ZIF，不仅保留了传统MOF材料的大比表面积、可调孔径和高结晶度的特点，还因为银离子使银基ZIF具备一定抗菌效果，增强功能层的抗菌特性；由于银基ZIF具备的大比表面积、大孔径的特点，能够共价接枝更多的溶菌酶，并依旧具备优异的广谱抗菌性能；银基ZIF材料与溶菌酶协同增强功能层的杀菌能力，起到长效杀菌、抑菌效果好、消除异味的作用，进一步改善车内空气质量，为乘客提供更为健康、清新的乘车环境。The present invention provides a material for automobile lining with sterilization and deodorization and a preparation method thereof. The material for automobile lining includes a surface layer, a functional layer and a bottom layer arranged in sequence, and the functional layer is obtained by surface treating the fabric with a MOF-lysozyme material. The silver-based ZIF formed by silver ions and dimethylimidazole not only retains the characteristics of large specific surface area, adjustable pore size and high crystallinity of traditional MOF materials, but also because of the silver ions, the silver-based ZIF has a certain antibacterial effect, and enhances the antibacterial properties of the functional layer; due to the large specific surface area and large pore size of the silver-based ZIF, more lysozyme can be covalently grafted, and still has excellent broad-spectrum antibacterial properties; the silver-based ZIF material and lysozyme synergistically enhance the bactericidal ability of the functional layer, play a role in long-term sterilization, good antibacterial effect, and elimination of odor, further improve the air quality in the car, and provide passengers with a healthier and fresher riding environment.

Description

Material with sterilization and peculiar smell removal functions for automobile lining and preparation method thereof
Technical Field
The invention belongs to the technical field of automotive interiors, and particularly relates to a material with sterilization and peculiar smell removal for an automotive liner and a preparation method thereof.
Background
With the rapid development of economy and the continuous improvement of the living standard of people, the automobile industry is also facing the unprecedented prosperous times. The requirements of people on automobiles are not limited to the beautiful quality, functions and appearance of the whole automobile, but are expanded to the comfort and health of the environment in the automobile.
The automobile roof inner decorative board is used as the largest decorative surface in the automobile, and the structure of the automobile roof inner decorative board is generally formed by compounding various materials such as a fabric, a glass fiber felt, a foam material, a non-woven fabric and the like. The traditional non-woven fabric decorative layer is widely applied due to soft texture and convenient processing, but simultaneously, the material is easy to accumulate dust and moisture, thereby providing ideal growth conditions for bacteria and viruses. Particularly in the environment with higher humidity or moderate temperature, the propagation speed of bacteria can be further accelerated, so that the problem of sanitation in the vehicle is increasingly serious. Therefore, how to improve the environment in the vehicle, timely and effectively kill or inhibit microorganisms such as bacteria and viruses, and improve the air quality in the vehicle has become a key problem to be solved currently.
Under the current situation, the industry gradually explores and promotes the use of automobile roof interior trim materials with a sterile function. The antibacterial material is generally prepared by adding an antibacterial agent into a traditional non-woven fabric, fabric or composite material, or adopting a nano technology to perform antibacterial coating treatment on the surface of the material, so that a protective layer capable of effectively inhibiting bacterial growth is formed on the surface of the material. Common antimicrobial techniques include silver ion antimicrobial, zinc oxide and titanium dioxide nanocoating, and other bioactive applications, which can maintain the antimicrobial effect of the interior trim panel for a longer period of time, reducing bacterial and viral proliferation. Meanwhile, the aseptic materials can also effectively inhibit peculiar smell generated by decomposing organic matters by bacteria, thereby further improving the air quality in the vehicle and providing more healthy and fresh riding environment for passengers.
However, while the use of sterile materials in automotive interiors has significant advantages, there are also problems and challenges in practical popularization. First, the physical properties and durability of the material can be affected to some extent by the addition of antimicrobial agents or the application of nanocoating. For example, some of the antibacterial agents may gradually fail in long-term use, resulting in attenuation of antibacterial performance, while some of the nanocoating layers may undergo flaking or aging under repeated rubbing, uv irradiation, or temperature changes, thereby reducing the overall antibacterial effect of the interior trim panel. Second, the relatively high cost of producing sterile materials, and some high-end technologies have not achieved large-scale low-cost applications, which has led automobile manufacturers to trade-off performance versus cost in selecting materials. In addition, some antibiotic additives may have a certain safety hazard in long-term contact with human body or in high-temperature environment, and mobility and toxicity problems of the antibiotic additives need to be paid attention to. Finally, environmental regulations are increasingly strict, and environmental protection performance and sustainability of part of traditional antibacterial agents are questioned, which promotes industry to continuously seek new green and environmental-friendly antibacterial materials in the research and development process.
In general, along with the continuous improvement of the environmental health requirements of people in vehicles, the sterile interior material is an emerging technology, and has very broad application prospects in automobile roofs and other interior parts.
Disclosure of Invention
The invention aims to provide a material for an automobile lining with the functions of sterilizing and deodorizing, and a preparation method thereof.
The technical scheme of the invention is as follows:
in a first aspect, the invention provides a material for an automobile inner liner with sterilization and peculiar smell removal functions, which comprises a surface layer, a functional layer and a bottom layer which are sequentially arranged, wherein the functional layer is obtained by subjecting a fabric to surface treatment of a MOF-lysozyme material.
In some embodiments, the facing may be selected from one or more combinations of nonwoven, nonwoven paper, or cotton fibers.
In some embodiments, the method of preparing the MOF-lysozyme material comprises the steps of:
s1, dissolving silver nitrate hexahydrate and dimethyl imidazole in a solvent, heating for reaction, cooling to room temperature after the reaction is finished, separating out crystals, washing the crystals, and drying to obtain a silver-based ZIF material;
s2, carrying out ultrasonic dispersion on the silver-based ZIF material by using a sterile solvent, adding 3-aminopropyl triethoxysilane into the dispersion liquid, stirring at room temperature for reaction, and washing and drying for later use after the reaction is finished;
S3, dispersing the product obtained by the step S2 in phosphate buffer solution, adding glutaraldehyde to react at room temperature, centrifuging and washing after the reaction, adding the mixture into lysozyme solution, carrying out gentle shaking reaction, centrifuging to separate the product, washing and drying at low temperature to obtain the MOF-lysozyme material.
In some embodiments, the silver nitrate hexahydrate and dimethylimidazole are added in a molar ratio of 1:5-10. The molar ratio of metal ions to ligands can influence the crystal morphology and performance of the silver-based ZIF material, correspondingly influence the content of the covalent grafted lysozyme, and has a direct relation with the final antibacterial effect.
In some embodiments, the heating of S1 is performed at a temperature of 40-60 ℃ for a reaction time of 12-24 hours.
In some embodiments, the silver-based ZIF material and the 3-aminopropyl triethoxysilane are added in a mass ratio of 1:0.01-0.05, and the 3-aminopropyl triethoxysilane forms an amino coating layer on the ZIF surface.
In some embodiments, the glutaraldehyde is added in an amount of 2-4% of the 3-aminopropyl triethoxysilane. Reacting with surface amine groups to generate terminal active aldehyde groups.
In some embodiments, the lysozyme solution is a PBS buffer containing lysozyme, the ph=7.4 of the PBS buffer, the content of lysozyme is 1-10 mg/mL.
In some embodiments, the specific steps of the surface treatment include:
washing the fabric with water to remove dust, immersing in ethanol solution for ultrasonic treatment to remove surface stains, taking out to obtain pretreated fabric, and finishing the MOF-lysozyme material on the fabric by an immersion method or a spraying method.
In some embodiments, the impregnation process may employ the steps of placing the pretreated fabric in a PBS buffer of MOF-lysozyme material, reacting for 1-2 hours at room temperature, then washing the fabric with deionized water, and drying at 40 ℃ for 1 finishing.
In some embodiments, the spraying process may employ the step of uniformly spraying a PBS buffer of MOF-lysozyme material onto the surface of the facing using a spray gun, and low temperature drying at 40 ℃.
In some embodiments, the number of finishing steps is 1-4 and the mass of MOF-lysozyme material finished per square centimeter of fabric per finishing step is 0.25-5g.
In a second aspect, the invention provides a preparation method of the material for automobile inner liners with sterilization and peculiar smell removal, which specifically comprises the following steps:
The surface layer, the functional layer and the bottom layer are sequentially arranged from top to bottom, aqueous polyurethane adhesive is uniformly coated among the layers, and the aqueous polyurethane adhesive is subjected to pressure curing at the temperature of 20-40 ℃ for 12-24 hours, so that the material with the functions of sterilization and peculiar smell removal for the automobile lining is obtained.
In some embodiments, the coating mode may be one or more of knife coating, spray coating or roller coating, and may be specifically selected according to the type and thickness of the fabric.
The beneficial effects are that:
1. The silver-based ZIF formed by silver ions and dimethyl imidazole not only maintains the characteristics of large specific surface area, adjustable aperture and high crystallinity of the traditional MOF material, but also has a certain antibacterial effect due to the silver ions, and the antibacterial characteristic of the functional layer is enhanced.
2. Because of the characteristics of large specific surface area and large aperture of the silver-based ZIF, more lysozyme can be covalently grafted, and the silver-based ZIF still has excellent broad-spectrum antibacterial performance.
3. The silver-based ZIF material and lysozyme synergistically enhance the sterilization capability of the functional layer, play roles of long-acting sterilization, good antibacterial effect and peculiar smell elimination, further improve the air quality in a vehicle and provide a healthier and fresh riding environment for passengers.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
The chemical reagents used in the invention are all common commercial analytical pure unless specified.
The lysozyme solution used in the examples was 1mg/mL PBS (pH 7.4) solution.
The aqueous polyurethane adhesive used in the examples was purchased from Anhui Zhongen chemical Co., ltd., trade name PU1179.
PET used in the examples was purchased from DuPont, U.S. under the trademark RE5264.
The PP used in the examples was purchased from Wanhua chemistry under the designation EP548R.
Preparation example of MOF-lysozyme Material 1
S1, respectively dissolving 0.1 mol of silver nitrate hexahydrate and 1mol of dimethyl imidazole in a 100mL methanol solvent, uniformly stirring to obtain a dimethyl imidazole solution and a silver nitrate hexahydrate solution respectively, slowly dripping the dimethyl imidazole solution into the silver nitrate hexahydrate solution, heating the solution to 40 ℃ for reaction for 20 hours, cooling the reaction solution to room temperature after the reaction is finished, centrifuging the reaction solution at 5000rpm for 10 minutes to collect crystals, washing the crystals, and drying the crystals to obtain the silver-based ZIF material;
S2, weighing 50mg of the silver-based ZIF material, performing ultrasonic dispersion for 10 minutes by using 50ml of sterile solvent (sterile ethanol/water mixed solution with the volume ratio of 1:2), adding 0.5mg of 3-aminopropyl triethoxysilane into the dispersion, stirring at room temperature for reaction for 2 hours, and washing and drying for later use after the reaction is finished;
S3, dispersing 10mg of the product obtained by S2 preparation into 10ml of phosphate buffer solution (PBS, pH 7.4), adding 0.02mg of glutaraldehyde, reacting for 2 hours at room temperature, centrifuging and washing after the reaction, adding the mixture into 20ml of lysozyme solution, gently oscillating and reacting for 6 hours, separating the product by a centrifugal method, washing and drying at a low temperature to obtain the MOF-lysozyme material 1.
Preparation example of MOF-lysozyme Material 2
The preparation example of MOF-lysozyme material 1 was basically the same, except that the molar amounts of silver nitrate hexahydrate and dimethyl imidazole added were 0.1mol and 0.5mol, respectively, to prepare MOF-lysozyme material 2.
Preparation example of MOF-lysozyme Material 3
The preparation example of MOF-lysozyme material 1 was basically the same, except that the molar amounts of silver nitrate hexahydrate and dimethylimidazole added were 0.1mol and 1.5mol, respectively, to prepare MOF-lysozyme material 3.
Preparation example of MOF-lysozyme Material 4
S1, respectively dissolving 0.1 mol of silver nitrate hexahydrate and 1mol of dimethyl imidazole in a 100mL methanol solvent, uniformly stirring to obtain a dimethyl imidazole solution and a silver nitrate hexahydrate solution respectively, slowly dripping the dimethyl imidazole solution into the silver nitrate hexahydrate solution, heating the solution to 40 ℃ for reaction for 20 hours, cooling the reaction solution to room temperature after the reaction is finished, centrifuging the reaction solution at 5000rpm for 10 minutes to collect crystals, washing the crystals, and drying the crystals to obtain the silver-based ZIF material;
S2, adding 10mg of the silver-based ZIF material prepared by S1 into 20ml of lysozyme solution, gently oscillating for reaction for 6 hours, separating the product by a centrifugal method, washing and drying at low temperature to obtain the MOF-lysozyme material 4.
Preparation example of silver-based ZIF Material
Dissolving 0.1mol of silver nitrate hexahydrate and 1mol of dimethyl imidazole in 100 mL of methanol solvent respectively, uniformly stirring to obtain a dimethyl imidazole solution and a silver nitrate hexahydrate solution respectively, slowly dripping the dimethyl imidazole solution into the silver nitrate hexahydrate solution, heating to 40 ℃ for reaction for 20 hours, cooling to room temperature after the reaction is finished, centrifuging the reaction solution at 5000rpm for 10 minutes to collect crystals, washing the crystals, and drying to obtain the silver-based ZIF material.
The MOF-lysozyme material 1, the MOF-lysozyme material 2, the MOF-lysozyme material 3, the MOF-lysozyme material 4, the silver-based ZIF material and lysozyme are respectively subjected to surface treatment on a non-woven fabric, and the treatment steps are as follows:
Washing the fabric with water to remove dust, immersing in ethanol solution for 30min, ultrasonic treating to remove surface stains, taking out, air drying to obtain pretreated fabric, cutting the pretreated fabric into square pieces of 2cm multiplied by 2cm, respectively placing in 200ml PBS buffer solution containing 10g MOF-lysozyme material 1, MOF-lysozyme material 2, MOF-lysozyme material 3, MOF-lysozyme material 4, silver-based ZIF material and lysozyme, soaking at room temperature for 2h, washing the fabric with deionized water, drying at 40 ℃ for 1 time, finishing the fabric repeatedly for 4 times, finishing, and sequentially obtaining functional layers 1-6.
Examples and comparative examples
The surface layer, the functional layer and the bottom layer are sequentially arranged from top to bottom, aqueous polyurethane adhesive is uniformly coated among the layers, and the aqueous polyurethane adhesive is subjected to pressure curing at the temperature of 40 ℃ for 24 hours, so that the material for the automobile inner liner is respectively obtained. The specific materials are shown in table 1.
TABLE 1
Performance test:
1. The antibacterial performance is tested according to QB/T2591 2003 antibacterial Plastic antibacterial performance test method and antibacterial effect standard, and the test strains are Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 6528).
2. The test sample was placed in a beaker containing 1000 mL distilled water, then the beaker was placed in a water bath at 40 ℃ and stirred with a stirrer continuously, the water was changed every 12 hours, the antibacterial efficiency of the sample against escherichia coli and staphylococcus aureus after 240 hours and 720 hours of soaking was measured, and the retention rate of the antibacterial efficiency at 720 hours was calculated.
The results obtained are shown in Table 2.
TABLE 2
The embodiment and the comparative example show that the material for the automobile lining provided by the invention has excellent antibacterial effect and antibacterial stability, the initial antibacterial efficiency is high and can reach 99.9%, and after the material is subjected to water bath and stirring treatment for 720 hours, the antibacterial efficiency retention rate can reach 96-97%, and the material for the automobile lining provided by the invention can effectively improve the antibacterial efficiency and the antibacterial stability by preparing the silver-based MOF-lysozyme material, can be used for improving the antibacterial effect of the material for the automobile lining, and has high-efficiency and durable antibacterial performance.
Specifically, as can be seen from comparison of comparative example 1 with examples, the silver-based ZIF material prepared in comparative example 1 has smaller surface area, less amount of covalently grafted lysozyme and reduced initial antibacterial efficiency, and the MOF-lysozyme material 4 in comparative example 2 has no surface treatment of 3-aminopropyl triethoxysilane and glutaraldehyde in the preparation process, and the grafted lysozyme cannot be well fixed on the surface of the silver-based ZIF material, and the initial antibacterial efficiency can reach 99%, but after repeated oscillating and washing, the antibacterial efficiency of the material is attenuated to about 77%, and the antibacterial stability is poor.
Compared with the examples, the comparison of the comparative examples 3-4 shows that the functional layer prepared by singly using the silver-based ZIF material or the fabric treated by the lysozyme has inferior antibacterial effect and antibacterial stability compared with the product obtained by the examples, so that the silver-based ZIF material and the lysozyme can synergistically enhance the sterilizing capacity of the functional layer, play the roles of long-acting sterilization, good antibacterial effect and peculiar smell elimination, further improve the air quality in the vehicle and provide more healthy and fresh riding environment for passengers.
Those of ordinary skill in the art will recognize that the embodiments herein are intended to assist the reader in understanding the principles of the invention and should be understood that the scope of the invention is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.

Claims (10)

1. The material for the automobile inner liner with the functions of sterilization and peculiar smell removal comprises a surface layer, a functional layer and a bottom layer which are sequentially arranged, and is characterized in that the functional layer is obtained by performing surface treatment on a fabric by using an MOF-lysozyme material;
the preparation method of the MOF-lysozyme material comprises the following steps:
s1, dissolving silver nitrate hexahydrate and dimethyl imidazole in a solvent, heating for reaction, cooling to room temperature after the reaction is finished, separating out crystals, washing the crystals, and drying to obtain a silver-based ZIF material;
s2, carrying out ultrasonic dispersion on the silver-based ZIF material by using a sterile solvent, adding 3-aminopropyl triethoxysilane into the dispersion liquid, stirring at room temperature for reaction, and washing and drying for later use after the reaction is finished;
S3, dispersing the product obtained by the step S2 in phosphate buffer solution, adding glutaraldehyde to react at room temperature, centrifuging and washing after the reaction, adding the mixture into lysozyme solution, carrying out gentle shaking reaction, centrifuging to separate the product, washing and drying at low temperature to obtain the MOF-lysozyme material.
2. The automotive lining material according to claim 1, wherein the face material is selected from one or more combinations of nonwoven fabrics, nonwoven papers or cotton fibers.
3. The material for automobile inner liners according to claim 1, characterized in that the addition molar ratio of silver nitrate hexahydrate to dimethylimidazole is 1:5-10.
4. The material for automobile inner liners according to claim 1, wherein the heating of S1 is performed at a heating temperature of 40-60 ℃ for a reaction time of 12-24 hours.
5. The material for automobile inner liners according to claim 1, wherein the addition mass ratio of the silver-based ZIF material to the 3-aminopropyl triethoxysilane is 1:0.01-0.05.
6. The material for automobile inner liners according to claim 1, wherein the glutaraldehyde is added in an amount of 2 to 4% by mass based on the 3-aminopropyl triethoxysilane.
7. The material for automobile inner liners according to claim 1, wherein the lysozyme solution is a PBS buffer containing lysozyme, the pH of the buffer=7.4, and the content of lysozyme is 1-10 mg/mL.
8. The automotive lining material according to claim 1, characterized in that the specific step of the surface treatment comprises:
washing the fabric with water to remove dust, immersing in ethanol solution for ultrasonic treatment to remove surface stains, taking out to obtain pretreated fabric, and finishing the MOF-lysozyme material on the fabric by an immersion method or a spraying method.
9. The material for automobile inner liners according to claim 8, wherein the number of finishing times is 1-4, and the mass of MOF-lysozyme material finished per square centimeter of fabric in each finishing step is 0.25-5g.
10. The method for producing a material for automobile inner liners according to any one of claims 1 to 9, characterized by comprising the steps of:
The surface layer, the functional layer and the bottom layer are sequentially arranged from top to bottom, aqueous polyurethane adhesive is uniformly coated among the layers, and the aqueous polyurethane adhesive is subjected to pressure curing at the temperature of 20-40 ℃ for 12-24 hours, so that the material with the functions of sterilization and peculiar smell removal for the automobile lining is obtained.
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